Capture of gases emitted from power plants is an area of increasing interest. Power plants based on the combustion of fossil fuels (such as petroleum, natural gas, or coal) generate carbon dioxide as a by-product of the reaction. Historically this carbon dioxide has been released into the atmosphere after combustion. However, it is becoming increasingly desirable to identify ways to find alternative uses for the carbon dioxide generated during combustion.
One option for managing the carbon dioxide generated from a combustion reaction is to use a capture process to separate the CO2 from the other gases in the combustion exhaust. An example of a traditional method for capturing carbon is passing the exhaust stream through an amine scrubber. While an amine scrubber can be effective for separating CO2 from an exhaust stream, there are several disadvantages. In particular, energy is required to operate the amine scrubber and/or modify the temperature and pressure of the exhaust stream to be suitable for passing through an amine scrubber. The energy required for CO2 separation reduces the overall efficiency of the power generation process.
In order to offset the power required for CO2 capture, one option is to use a molten carbonate fuel cell to assist in CO2 separation. The fuel cell reactions that cause transport of CO2 from the cathode portion of the fuel cell to the anode portion of the fuel cell can also result in generation of electricity. However, conventional combinations of a combustion powered turbine or generator with fuel cells for carbon separation have resulted in a net reduction in power generation efficiency per unit of fuel consumed.
An article in the Journal of Fuel Cell Science and Technology (G. Manzolini et. al., J. Fuel Cell Sci. and Tech., Vol. 9, February 2012) describes a power generation system that combines a combustion power generator with molten carbonate fuel cells. Various arrangements of fuel cells and operating parameters are described. The combustion output from the combustion generator is used in part as the input for the cathode of the fuel cell. This input is supplemented with a recycled portion of the anode output after passing through the anode output through a cryogenic CO2 separator.
One goal of the simulations in the Manzolini article is to use the MCFC to separate CO2 from the power generator's exhaust. The simulation described in the Manzolini article establishes a maximum outlet temperature of 660° C. and notes that the inlet temperature must be sufficiently cooler to account for the temperature increase across the fuel cell. The electrical efficiency (i.e. electricity generated/fuel input) for the MCFC fuel cell in a base model case is 50%. The electrical efficiency in a test model case, which is optimized for CO2 sequestration, is also 50%.
An article by Desideri et al. (Intl. J. of Hydrogen Energy, Vol. 37, 2012) describes a method for modeling the performance of a power generation system using a fuel cell for CO2 separation. Recirculation of anode exhaust to the anode inlet and the cathode exhaust to the cathode inlet are used to improve the performance of the fuel cell. Based on the model and configuration shown in the article, increasing the CO2 utilization within the fuel cell is shown as being desirable for improving separation of CO2. The model parameters describe an MCFC electrical efficiency of 50.3%.
U.S. Pat. No. 7,396,603 describes an integrated fossil fuel power plant and fuel cell system with CO2 emissions abatement. At least a portion of the anode output is recycled to the anode input after removal of a portion of CO2 from the anode output.
Molten carbonate fuel cells utilize hydrogen and/or other fuels to generate electricity. The hydrogen may be provided by reforming methane or other reformable fuels in a steam reformer that is upstream of the fuel cell or within the fuel cell. Reformable fuels can encompass hydrocarbonaceous materials that can be reacted with steam and/or oxygen at elevated temperature and/or pressure to produce a gaseous product that comprises hydrogen. In particular, reformable fuel can include, but is not limited to, alkanes, alkenes, alcohols, aromatics, and/or other carbonaceous and organic compounds that can be reformed to generate H2 and carbon oxides (either CO or CO2). Alternatively or additionally, fuel can be reformed in the anode cell in a molten carbonate fuel cell, which can be operated to create conditions that are suitable for reforming fuels in the anode. Alternately or additionally, the reforming can occur both externally and internally to the fuel cell.
Traditionally, molten carbonate fuel cells are operated to maximize electricity production per unit of fuel input, which may be referred to as the fuel cell's electrical efficiency. This maximization can be based on the fuel cell alone or in conjunction with another power generation system. In order to achieve increased electrical production and to manage the heat generation, fuel utilization within a fuel cell is typically maintained at 70% to 75%.
U.S. Published Patent Application 2011/0111315 describes a system and process for operating fuel cell systems with substantial hydrogen content in the anode inlet stream. The technology in the '315 publication is concerned with providing enough fuel in the anode inlet so that sufficient fuel remains for the oxidation reaction as the fuel approaches the anode exit. To ensure adequate fuel, the '315 publication provides fuel with a high concentration of H2. The H2 not utilized in the oxidation reaction is recycled to the anode for use in the next pass. On a single pass basis, the H2 utilization may range from 10% to 30%. The '315 reference does not describe significant reforming within the anode, instead relying primarily on external reforming.
U.S. Published Patent Application 2005/0123810 describes a system and method for co-production of hydrogen and electrical energy. The co-production system comprises a fuel cell and a separation unit, which is configured to receive the anode exhaust stream and separate hydrogen. A portion of the anode exhaust is also recycled to the anode inlet. The operating ranges given in the '810 publication appear to be based on a solid oxide fuel cell. Molten carbonate fuel cells are described as an alternative.
U.S. Published Patent Application 2003/0008183 describes a system and method for co-production of hydrogen and electrical power. A fuel cell is mentioned as a general type of chemical converter for converting a hydrocarbon-type fuel to hydrogen. The fuel cell system also includes an external reformer and a high temperature fuel cell. An embodiment of the fuel cell system is described that has an electrical efficiency of about 45% and a chemical production rate of about 25% resulting in a system coproduction efficiency of about 70%. The '183 publication does not appear to describe the electrical efficiency of the fuel cell in isolation from the system.
U.S. Pat. No. 5,084,362 describes a system for integrating a fuel cell with a gasification system so that coal gas can be used as a fuel source for the anode of the fuel cell. Hydrogen generated by the fuel cell is used as an input for a gasifier that is used to generate methane from a coal gas (or other coal) input. The methane from the gasifier is then used as at least part of the input fuel to the fuel cell. Thus, at least a portion of the hydrogen generated by the fuel cell is indirectly recycled to the fuel cell anode inlet in the form of the methane generated by the gasifier.